Hydrocarbon oil and method of making the same



Patented June 11, 1935 UNITED STATES PATENT OFFICEV HYDROOABBON OIL AND IllETHOD OF MAKING THE SAME Herbert G. M. Fischer, Westfleld, and Cliflord E.

Gustaison, Elizabeth, an! Oil Development of Delaware N. J., assignors to Stand- Company, a corporation No Drawing. Application September 21, 1928, V Serial No. 307,545

12 Claims.

ured by the method No. 530.1 in the United States Bureau of Mines Technical Paper 323 B, entitled Specification for petroleum products and methods of testing, revised October 21, 1927, page 96. In brief, this methodconsists in placing 100 cc. of the naphtha to be tested in a 3 inch diameter spun copper dish on a steam bath and evaporating oif the volatile material. The result is expressed in milligrams of gum left in the dish per- 100 cc. of naphtha.

As noted above, naphthas containing relatively large quantities of gum are objectionable, particularly for motor fuels, cleaning naphtha, light solvents and the like. It is also well known that on standing the gum content of many naphthas steadily increases. We have discovered that the addition of certain organic materials to the naphtha even though in very small quantities greatly reduces the gum as indicated by the above described test and also prevents an increase'of gum for prolonged, if not for indefinite periods.

In general, aromatic hydrocarbons with condensed rings (polycyclic compounds) are suitable for our process such as naphthalene, anthracene, phenanthrene and the like and certain derivatives of these compounds are also useful for our purpose. The substitution of certain groups, particularly those of a basic character, in the alpha position greatly increases the eflect of the addition agents, for example, alpha-naphthol appears to be better than naphthalene as also are alphanaphthylamine and phenyl alpha-naphthylamine.

The quantity of the addition agent is very small, not being greater in any case than 5 gr. per litre of the naphtha and generally between the approximate limits of .01 to 1.0 gr. per litre. There appears to be an optimum quantity of the agent which will give the best results and it is a simple matter to make up samples of the different strengths and empirically select the most suitable concentration. This behavior appears to be characteristic of all suitable addition agents including those disclosed in our copending application Serial No. 307,546, filed Sept. 21, 1928. As an illustration, the following example is given, alphanaphthol being added in different quantities as indicated and opposite the number of milligrams of gum per 100 cc. of naphtha is given as deter- 5 mined by the above described test.

- Gum Original cracked naphtha 280 mg./100 cc. Naphtha .5 gr. CroHmOH/litre- 12 m The reagent may be dissolved directly in the oil or may be added in the form of a more concentrated solution in naphtha, benzol or other suitable solvents. The agent should be added to the gasoline, which is preferably slightly alkaline or neutral and no treatment which will remove the agent should thereafter be given the oil.

We have observed that mixtures-of addition agents such as alpha-naphthol and naphthylamine may be added to gasoline with good results and that volatile metal compounds such as metal carbonyls, metallo-organic substances, which are useful for their anti-detonation effects, may be present in the naphtha without any adverse action.

Asexamples of othermaterials the following tests are given:

Mg. Original cracked naphtha 231 3 Original naphtha+alpha-naphthol 5 Original naphtha+phenyl alphanaphthylamine 22 Original naphtha-l-naphthylamine 24 The agents are in proportion of .l/gr. per litre of naphtha.

In other tests it has been found that in addition to reducing general gum formation, these agents also reduce acid formation on standing and in one such test the original gasoline is 45 found to have a gum test 015-1227 mg./ cc. after 3 weeks storage while a comparative sample which contained an addition agent shows only 7.2 mg. The acidity of the first sample is 28.95 as against 0.0 of the second after 3 weeks. 50 The acidity is given in grams of NaOH per barrel of oil and it should be noted that both samples were of the same oil and both were neutral at the beginning of the test. 7

In the following claims the term' naphthalene compounds having certain substituted groups is used and by this term we wish to include the substituted naphthalene itself, and the substituted homologues, of which phenyl naphthalene may be taken as an example.

Our invention is not to be limited by any theory of the mechanism of the process nor by any example given merely by way of illustration but only by the following claims in which we wish to claim all novelty inherent in the invention. We do not claim herein the use of eipbenaphthol or alpha-naphthyiamine alone as gum inhibitors in gasoline nor the use of the class of substances composed of alpha hydroxyl and amino compounds oi naphthalene hydrocarbons since those inventions are claimed in application Serial No. 652,420 filed January 18, 1933 by Herbert G. M. Fischer.

We c:

l. A composition of matter comprising a low boiling hydrocarbon oil containing unsaturated constituents of the type normally tending to form gum and produced by pyrolysis of heavy hydrocarbons, to which has been added an ciphenaphthylamine having one hydrogen oi the amino group substituted by a benzene hydrocarbon radical, in quantity sufilcient to retard such deterioration.

2. A composition of matter comprising a low boiling hydrocarbon oil containing unsaturated constituents of the-type normally tending to form gum and produced by pyrolysis of heavy hydrocarbons, to which has been added a. phenyl alpha-naphthylamine in quantity suiflcient to retard such' gum formation.

3. The method of preserving low boiling hydrocarbon oils containing unsaturated constituents of the type normally tending to form gum and produced by pyrolysis of heavy hydrocarbons, which comprises incorporating therein a snail amount of an alpha-naphthylamine having one hydrogen or the amino group substituted by a benzene hydrocarbon radical, in quantity sumcient to retard such deterioration.

, 4. The method of preserving low boiling hydrocerbon'oils containing unsaturated constituents oi: the type normally tending to form gum and produced by pyrolysis of heavy hydrocarbons, which comprises incorporating therein a. small proportion of a phenyl elpha-naphthylamine.

5. The method of preserving cracked naphtha normally tending to deteriorate and form gums on storage, which comprises incorporating therewith 0.1 to 5 grams per litre of phenyl alphanephthylamine. v 6. A motor fuel comprising cracked gasoline normally tending to deteriorate upon storage to which has been added a phenylmpha naphthylamine in quantity suilicient to retard such deterioration.

'2. A motor fuel comprising cracked gasoline normally tending to deteriorate upon storage to which has been added phenyl alpha naphthylee in quantity suiilcient to retard such deterioration.

8. A motor fuel comprising cracked gasoline normally tending to develop gum on storage to which has been added phenyl alpha naphthylamine in quantity suflicient to retard the formation of gum.

9. A cracked gasoline normally tending to develop gum to which has been added phenyl alpha naphthylamine in quantity suiiicient to retard the formation of gum.

- 10. A motor fuel comprising a gasoline normally tending to deteriorate upon storage to which has been added phenyl alpha naphthylamine in quantity suiiicient to retard such deterioration.

11. A compodtion of matter comprising a low boiling hydrocarbon oil of the class produced by thermal decomposition of hydrocarbon of higher molecular weight normally tending to form gum, and 0.01-5 grams per liter of phenyl alpha n'hphthylamine 12. A composition of matter comprisingcracked naphtha normally tending to form gum, and 0.01-1 gram per liter of phenyl alpha naphthylamine. r

G. M. FISCHER. CHM-0RD E. GUSTAFSON.

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